CN105000917A - Preparation method of mullite oxidation resistant coating - Google Patents
Preparation method of mullite oxidation resistant coating Download PDFInfo
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- CN105000917A CN105000917A CN201510500693.5A CN201510500693A CN105000917A CN 105000917 A CN105000917 A CN 105000917A CN 201510500693 A CN201510500693 A CN 201510500693A CN 105000917 A CN105000917 A CN 105000917A
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Abstract
The invention relates to a preparation method of a mullite oxidation resistant coating, particularly to a method for preparing a mullite/SiC bilayer-structure oxidation resistant coating on the surface of a carbon/carbon composite material. The preparation method comprises the following steps: pre-calcining mullite powder A and mullite precursor powder B according to the mass ratio of (4-6):1 to prepare pre-calcined mullite powder A and mullite precursor powder B, preparing a coalescing agent and a drying inhibitor according to certain ratio, uniformly mixing the pre-calcined mullite powder A, the pre-calcined mullite precursor powder B, the coalescing agent and the drying inhibitor to obtain a sizing agent, dipping a matrix in the sizing agent, performing sizing agent coating by adopting the dip-coating technology, and after the sizing agent coating, calcining at 1480-1515 DEG C to obtain the mullite oxidation resistant coating. According to the invention, the technology is simple, the raw material is cheap and available, the industrial production is facilitated, and the obtained coating has the advantages of high uniformity and compactness, excellent binding property, and high high-temperature oxidation resistant capacity.
Description
Technical field
The present invention relates to a kind of preparation method of mullite oxidation resistant coating; Prepare the method for mullite/SiC bilayer structure oxidation resistant coating at surface of carbon/carbon composite in particular to one.
Background technology
Carbon/carbon compound material is owing to possessing a series of excellent characteristic such as high-strength and high-modulus under low thermal coefficient of expansion, low density, high heat-conductivity conducting performance, high temperature and resistance to ablation, corrosion-resistant, stable friction factor, become a kind of high-temperature structural material having great potential and broad prospect of application, and be widely used in the industrial circles such as Aeronautics and Astronautics, energy petrochemical industry.But the oxidation onset temperature due to carbon/carbon compound material is only 450 DEG C, the oxidation deactivation therefore under high temperature oxidation stability atmosphere just becomes the one of the main reasons of restriction carbon/carbon compound material application development.The antioxygen property improving carbon/carbon compound material becomes the key expanding carbon/carbon compound material range of application.
Oxidation resistant coating technology be a kind of put into practice the most effective technological approaches of solution carbon/carbon compound material high-temperature oxidation resistant problem that proves.Oxidation resistant coating due to single layer structure is difficult to meet application requiring, and development coating system that is double-deck or multilayered structure has become an inexorable trend of oxidation resistant coating technical development.Because mullite ceramic has high-temperature-phase good stability, excellent in mechanical performance, anti-thermal shock/thermal cycling capability is strong, and the series of advantages such as erosion resistance environment, become the oxidation resistant coating material system that a class is desirable.In addition, because the thermal expansivity of mullite ceramic is very close with the thermal expansivity of SiC ceramic, both being combined can play respective advantage thus reach desirable protection effect.Therefore be prime coat with SiC ceramic, the Oxidation Resistant Coatings for Carbon/Carbon Composites structure of mullite ceramic to be external coating (EC) be constructional feature receives the extensive concern of investigator in recent years.
The technology of preparing of current main mullite coating has plasma spraying method, electro beam physics vapour deposition (EB-PVD), chemical vapour deposition (CVD) etc.Compare with traditional coating preparation means, the main tool of sol-gel method has the following advantages: the first, and processing unit is simple, and equipment cost is low; The second, it is fast that coating prepares speed, and production capacity is with the obvious advantage; 3rd, lower preparation temperature can be realized, avoid the thermal damage for body material in coating preparation process; 4th, strong to the design con-trol ability of material microstructure; 5th, require low to base shape, be more convenient for realizing preparing coating on complicated shape matrix.But current traditional sol-gel preparation technology of coating also also exists a lot of deficiency, constrains its development and application.Main defect has: 1) coating is loose porous, and density is low; 2) between coating and matrix in conjunction with poor, coating is easy to crack in dry or sintering process peels off; 3) the coat-thickness upper limit is low, is difficult to the thickness requirement meeting oxidation resistant coating; 4) preparation process need experience repeatedly coating-drying-sintering process, is difficult to the coating of the even compact being prepared ideal thickness by single application.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned prior art, by combining dipping-lift technology and sol-gel technology, provide and a kind ofly once to complete coating preparation and without the need to repeatedly circulation and Post isothermal treatment, have that preparation cost is low, the cycle is short, simple operation and other advantages.
The preparation method of a kind of mullite oxidation resistant coating of the present invention, comprises the steps:
Step one
With aluminum soluble salt, silicon ester be raw material, in molar ratio, Al:Si: organic solvent: catalyzer=(2 ~ 3): (1 ~ 1.5): (4 ~ 9): (0.3 ~ 0.5), joins and carries out back flow reaction after getting raw material, organic solvent, catalyzer and obtain gel; Gained gel after drying, under an oxygen-containing atmosphere, in 1200-1350 DEG C of calcining, obtains precalcining porzite powder A;
Step 2
With aluminum soluble salt, silicon ester be raw material, in molar ratio, Al:Si: organic solvent: catalyzer=(2 ~ 3): (1 ~ 1.5): (4 ~ 9): (0.3 ~ 0.5), join after getting raw material, organic solvent, catalyzer and carry out back flow reaction at 60-85 DEG C, and then instill deionized water; And be warming up to 80 ~ 85 DEG C of reactions cooling, ageing after at least 8 hours; After ageing, 80 ~ 120 DEG C of dryings, obtain mullite precursor powder material B;
Step 3
In mass ratio, precalcining porzite powder A: mullite precursor powder material B=4 ~ 6:1, join and get precalcining porzite powder A, mullite precursor powder material B, then join and get film coalescence aid, drying retarder, solvent; By join get precalcining porzite powder A, mullite precursor powder material B, film coalescence aid, drying retarder, solvent evenly after obtain slurry, matrix is immersed in slurry, utilizes Best-Effort request technology to carry out slurry coating; After having applied, 1480 ~ 1515 DEG C of calcinings, obtain mullite oxidation resistant coating.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In step one,
Described aluminum soluble salt is selected from the one in nine water aluminum nitrates, six water and aluminum chloride; The water reacting required in step one is provided by the crystal water in aluminium salt;
Described silicon ester is selected from least one in tetraethoxy, methyl silicate, positive silicic acid propyl ester;
Described organic solvent is selected at least one in dehydrated alcohol, anhydrous methanol;
Described catalyzer is selected from least one in Glacial acetic acid and hydrofluoric acid.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In step one, described back flow reaction is: under 45-75 DEG C of heating in water bath, be warming up to 80-100 DEG C of reaction 10-14h after back flow reaction 3-5h again, obtain gel.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In step one, after obtaining gel, at 80-120 DEG C of dry 8-72 hour; With 150-350rpm after drying, after ball milling 1-4 hour, carry out calcining 2-3 hour at 1200-1350 DEG C, cool to room temperature with the furnace, obtain precalcining porzite powder A.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In step 2;
Described aluminum soluble salt is selected from Burow Solution, Al (NO
3)
3at least one in 9H2O, Aluminum chloride anhydrous;
Described silicon ester is selected from least one in tetraethoxy, methyl silicate, positive silicic acid propyl ester;
Described organic solvent is selected at least one in dehydrated alcohol, anhydrous methanol;
Described catalyzer is selected from least one in Glacial acetic acid and hydrofluoric acid;
In the deionized water instilled and system, the mol ratio of aluminium element is 3 ~ 7:6.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In step 2
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In step 2;
Back flow reaction 4 ~ 6h is carried out, then at instillation deionized water at 60-85 DEG C; And be warming up to 80 ~ 85 DEG C of reactions cooling, ageing after at least 8 hours; During ageing, the period is 1 ~ 2 month, temperature is 40-65 DEG C; After ageing completes, after 100-120 DEG C of dry 10-14h, after 1-4 hour, obtain mullite precursor powder material B with 150-350rpm ball milling.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In step 3, in mass ratio, precalcining porzite powder A: mullite precursor powder material B=4 ~ 6:1, join and get precalcining porzite powder A, mullite precursor powder material B, and join 10 ~ 25wt% that the precalcining porzite powder A that gets and mullite precursor powder material B two kinds of powder total masses are solvent for use total mass; By join the 0.3-1.5% getting precalcining porzite powder A and mullite precursor powder material B total mass and join and get film coalescence aid; Described film coalescence aid is selected from least one in polyvinylpyrrolidone, polyvinyl butyral acetal; By 5 ~ 8wt% of solvent total mass, join and get drying retarder; Described drying retarder is selected from least one in oxalic acid, glycerol; Described solvent is selected from least one in dehydrated alcohol, anhydrous methanol, acetone.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; Its optimization technique technical scheme comprises the following steps:
Steps A
In molar ratio, Al (NO
3)
3the mol ratio of 9H2O, tetraethoxy, dehydrated alcohol and Glacial acetic acid is 3:1:5 ~ 8:0.3 ~ 0.5, joins and gets Al (NO
3)
39H
2o, tetraethoxy, dehydrated alcohol and Glacial acetic acid, mix, and under 45-75 DEG C of heating in water bath, is then warming up to 80-100 DEG C of reaction 10-14h after back flow reaction 3-5h again, obtains gel; Gained gel is at 80-120 DEG C of dry 8-72 hour; With 150-350rpm after drying, after ball milling 1-4 hour, carry out calcining 2-3 hour at 1200-1350 DEG C, cool to room temperature with the furnace, obtain precalcining porzite powder A;
Step B
In molar ratio, Burow Solution: Al (NO
3)
39H
2o: Aluminum chloride anhydrous: tetraethoxy=1.8:0.4:0.8:1; Join and get Burow Solution, Al (NO
3)
39H
2o, Aluminum chloride anhydrous, tetraethoxy;
Then, in molar ratio, glacial acetic acid: tetraethoxy=1 ~ 2:5 joins and gets glacial acetic acid,
The Burow Solution, the Al (NO that get will be joined
3)
39H
2o, Aluminum chloride anhydrous, tetraethoxy, glacial acetic acid are dissolved in dehydrated alcohol, under the environment of isolated moisture content, under 60-70 DEG C of heating in water bath after back flow reaction 3-5h, drip deionized water again, in the deionized water dripped and system, the mol ratio of aluminium element is 3 ~ 7:6, is warming up to 80-85 DEG C of reaction 8-12h subsequently; After reaction terminates by the gel that is obtained by reacting 40-65 DEG C of ageing 1 ~ 2 month, then after 100-120 DEG C of dry 10-14h to obtain mullite precursor powder material B after the rotating speed ball milling 1-4h of 200-300rpm; Burow Solution used, Al (NO
3)
39H
2in O, Aluminum chloride anhydrous, the mol ratio of aluminium element and dehydrated alcohol used is 3:5 ~ 8;
Step C
In mass ratio, precalcining porzite powder A: mullite precursor powder material B=4 ~ 6:1, preferably 4.8-5.5:1, join and get precalcining porzite powder A, mullite precursor powder material B, then join and get film coalescence aid, drying retarder, solvent; By join get precalcining porzite powder A, mullite precursor powder material B, film coalescence aid, drying retarder, solvent evenly after obtain slurry, matrix is immersed in slurry, utilizes Best-Effort request technology to carry out slurry coating; After having applied, 1480 ~ 1515 DEG C of calcinings, obtain mullite oxidation resistant coating; Described film coalescence aid is selected from least one in Polyvinylprrilone butyral, and the quality of used film forming auxiliary agent is the 0.8-1.2% of precalcining porzite powder A and mullite precursor powder material B total mass; Described solvent is made up of 7:3 ~ 5 by volume dehydrated alcohol and acetone, and join 10 ~ 25wt% that the precalcining porzite powder A that gets and mullite precursor powder material B two kinds of powder total masses are solvent for use total mass; ; Described siccative is oxalic acid, and consumption of oxalic acid is 5 ~ 8wt% of solvent total mass.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; When utilizing Best-Effort request technology to carry out slurry coating, the control rate of pulling is 05-3mm/min, and temperature is 40-50 DEG C.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; When utilizing Best-Effort request technology to carry out slurry coating, the nitrogen flow rate controlled in lift still is 1.0-2L/min, is preferably 1.5L/min.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; Described matrix is prepared by following proposal:
Step I
First by 60 ~ 65wt.%Si, 10 ~ 30wt.%SiC, 5 ~ 10wt.% powdered carbon, 1 ~ 5wt.%Al
2o
3be placed in ball grinder to take out after the rotary speed wet-milling 2-4h of 200-250r/min, be placed in loft drier dry 48-72h at 80-120 DEG C, sieve, obtain-60 object embedding powders;
Step II
Be embedded in loading in embedding powder in graphite tank and by C/C composite sample after in embedding powder, 2-2.5h is incubated be heated to 1750 DEG C-1800 DEG C in argon gas atmosphere in vacuum sintering furnace after, be cooled to room temperature, take out sample, at the ultrasonic cleaning of sample dehydrated alcohol is totally placed on 80-120 DEG C, after dry 2-4h, obtain SiC coating coated C/C composite sample (being described body material).
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In gained mullite external coating, the mol ratio of aluminium silicon can adjust according to demand.
The preparation method of a kind of mullite oxidation resistant coating of the present invention; In gained mullite external coating, the mol ratio of aluminium silicon is preferably 3:1.
Principle and advantage
The monocycle that present invention achieves coating is shaping, overcome sol-gel method prepare coating single application thickness low, easily peel off, need the shortcoming of repeatedly repetitive coatings-sintering period process.
The present invention adopts rational polycomponent coating materials material formula to design, by containing precalcining mullite miropowder, mullite precursor powder, film coalescence aid, drying retarder and mixed type solvent by reasonable component proportioning mixing after obtained novel coating slurry.This coating slurry significantly can improve ceramic pyrolysis productive rate and the limit coating thickness of coating slurry, eliminates the coating cracking phenomenon in sintering process, obtains fine and close flawless thick coating by single application.
The present invention is by adopting non-aqueous solvent, and the mode of strict isolation environment moisture, the synthesis controlling mullite precursor is carried out under non-fully hydrolyzed collosol-gelatin route, improves the sintering activity of mullite, control mullite particle pattern homogeneity, improve coating density.
The present invention is achieved by coating slurry and realizes fully dipping to matrix surface, and then greatly improves the bonding interface between mullite external coating and SiC bottom, thus avoids the appearance of disbonding phenomenon.Passing through accurately to control the processing parameters such as the rate of pulling, envrionment temperature and gas flow rate simultaneously, reach the object improving coating homogeneity and control drying rate, there is cracking phenomena with avoiding in drying process in the homogeneity improving coating.
In a word, the present invention passes through design of components cleverly, utilize the synergy of precalcining mullite miropowder, mullite precursor powder, film coalescence aid, drying retarder, the interworking effect especially between precalcining mullite miropowder, mullite precursor powder, achieves beyond thought effect.Gained finished product tool coating uniform, densification after once lifting coating, the advantages such as bonding properties is excellent, and high-temperature oxidation resistance is strong.
Accompanying drawing explanation
Accompanying drawing 1 is mullite external coating surface SEM photo prepared by the embodiment of the present invention 1;
Accompanying drawing 2 is the two coating cross sections SEM photo of mullite/SiC prepared by the embodiment of the present invention 1;
Accompanying drawing 3 is mullite external coating surface XRD figure spectrum prepared by the embodiment of the present invention 1;
Accompanying drawing 4 is the oxidation weight loss curve of the coated C/C matrix of mullite/SiC duplex coating under 1500 DEG C of atmospheric oxidations prepared by the embodiment of the present invention 1.
As can be seen from Figure 1 the mullite external coating surface compact flawless obtained by technique of embodiment 1 is adopted.
As can be seen from Figure 2 adopt the mullite external coating thickness obtained by technique of embodiment 1 to reach about 180 μm, and be combined well with SiC bottom.
As can be seen from Figure 3 adopt the mullite external coating obtained by technique of embodiment 1 primarily of 3/2 mullite and cristobalite phase composite.
As can be seen from Figure 4 mullite/SiC coated C/C the matrix material obtained by technique of embodiment 1 is adopted to have excellent antioxidant property under 1500 DEG C of atmospheric oxidation conditions.
Embodiment
Embodiment 1:
Entrapping method prepares SiC coating: first by 180g Si powder, 90g SiC powder, 15g powdered carbon, 15g Al
2o
3be placed in ball grinder to take out after the rotary speed wet-milling 24h of 200r/min, be placed in loft drier dry 12h at 90 DEG C, then with 60 object screen clothes sieve namely obtain embed powder.
Being embedded in loading in embedding powder in graphite tank and by C/C matrix sample after in embedding powder, being incubated 2h be heated to 1750 DEG C in argon gas atmosphere in vacuum sintering furnace after, after slowly cooling to room temperature, taking out sample.The coated C/C composite sample of SiC coating is obtained after dry 2h at the ultrasonic cleaning of sample dehydrated alcohol is totally placed on 90 DEG C.
Sol-gel method prepares mullite external coating:
1) by 10.4165g tetraethoxy and and 56.247gAl (NO
3)
39H
2o is dissolved in 14mL ethanol, under 60 DEG C of heating in water bath, 80 DEG C of reaction 12h after back flow reaction 4h, are warming up to again after adding 1.800g Glacial acetic acid, subsequently by after the gel drying be obtained by reacting to put into retort furnace after 250rpm rotating speed ball milling 2h, temperature rise rate 5 DEG C/min, room temperature is cooled to the furnace, obtained precalcining porzite powder A after 1200 DEG C of insulation 2h;
2) by 6.1233g aluminum acetate, 0.1500gAl (NO
3)
39H
2o, 12.4000g Aluminum chloride anhydrous and 10.4165g tetraethoxy are dissolved in after in 50mL dehydrated alcohol, add 1.2g Glacial acetic acid to stir as after catalyzer, be dissolved in completely after dehydrated alcohol until solid reagent and under 60 DEG C of heating in water bath, be slowly added dropwise to 0.042g deionized water again after back flow reaction 4h under isolated moisture content environment, be warming up to 80 DEG C of reaction 12h subsequently.Reaction terminate after by the gel ageing be obtained by reacting after 2 months after 120 DEG C of dry 12h to obtain mullite precursor powder material B after 250rpm rotating speed ball milling 2h;
3) after the dehydrated alcohol of 35mL and the acetone of 15mL being mixed, add 0.19g polyvinylpyrrolidone (PVP) to be stirred to and to dissolve completely, then add the oxalic acid of 15g precalcining porzite powder A, 3.75g mullite precursor powder material B and 2.5mL, obtain after ball milling 4h applying slurry under 250rpm rotating speed; 4) sample of coated for SiC C/C matrix material is immersed step 3) in the slurry that obtains, after once lifting coating, in tube furnace, obtain the coated C/C composite sample of mullite/SiC bilayer structure oxidation resistant coating after 1500 DEG C of sintering 2h.During lift coating, the control rate of pulling is 1mm/min, and lift envrionment temperature is 45 DEG C, and the nitrogen flow rate in lift still is 1.5L/min.Gained coating sample through 1500 DEG C, be oxidized 100h under air ambient after its rate of weight loss be only 0.38%.Its high temperature oxidation resistance is better than like product from far away.
Embodiment 2:
Entrapping method prepares SiC coating: first by 260g Si powder, 96g SiC powder, 40g powdered carbon, 4g Al
2o
3be placed in ball grinder to take out after the rotary speed wet-milling 24h of 200r/min, be placed in loft drier dry 12h at 90 DEG C, then with 60 object screen clothes sieve namely obtain embed powder.
Being embedded in loading in embedding powder in graphite tank and by C/C matrix sample after in embedding powder, being incubated 2h be heated to 1800 DEG C in argon gas atmosphere in vacuum sintering furnace after, after slowly cooling to room temperature, taking out sample.The coated C/C composite sample of SiC coating is obtained after dry 2h at the ultrasonic cleaning of sample dehydrated alcohol is totally placed on 90 DEG C.
Sol-gel method prepares mullite external coating:
1) by 41.666g tetraethoxy and and 224.988gAl (NO
3)
39H
2o is dissolved in 200mL ethanol, under 60 DEG C of heating in water bath, 80 DEG C of reaction 12h after back flow reaction 4h, are warming up to again after adding 30g Glacial acetic acid, subsequently by after the gel drying be obtained by reacting to put into retort furnace after 250rpm rotating speed ball milling 2h, temperature rise rate 5 DEG C/min, room temperature is cooled to the furnace, obtained precalcining porzite powder A after 1200 DEG C of insulation 2h;
2) by 60.6930g aluminum acetate, 3.7498gAl (NO
3)
39H
2o, 12.0000g Aluminum chloride anhydrous and 52.0852g tetraethoxy are dissolved in after in 200mL dehydrated alcohol, add 20g Glacial acetic acid to stir as after catalyzer, be dissolved in completely after dehydrated alcohol until solid reagent and under 60 DEG C of heating in water bath, be slowly added dropwise to 0.21g deionized water again after back flow reaction 4h under isolated moisture content environment, be warming up to 80 DEG C of reaction 12h subsequently.Reaction terminate after by the gel ageing be obtained by reacting after 2 months after 120 DEG C of dry 12h to obtain mullite precursor powder material B after 250rpm rotating speed ball milling 2h;
3) after the dehydrated alcohol of 35mL and the acetone of 15mL being mixed, add 0.5g polyvinylpyrrolidone (PVP) to be stirred to and to dissolve completely, then add the oxalic acid of 17g precalcining porzite powder A, 4.25g mullite precursor powder material B and 2.5mL, obtain after ball milling 4h applying slurry under 250rpm rotating speed; 4) sample with SiC coating C/C matrix material is immersed step 3) in the slurry that obtains, after once lifting coating, in tube furnace, obtain the coated C/C composite sample of mullite/SiC bilayer structure oxidation resistant coating after 1500 DEG C of sintering 2h.During lift coating, the control rate of pulling is 1mm/min, and lift envrionment temperature is 45 DEG C, and the nitrogen flow rate in lift still is 1.5L/min.The C/C composite sample that mullite/SiC bilayer structure oxidation resistant coating is coated is obtained after sintering 2h at 1500 DEG C after having applied in tube furnace.Gained coating sample through 1500 DEG C, be oxidized 100h under air ambient after its rate of weight loss be only 0.45%.Its high temperature oxidation resistance is better than like product from far away.
Claims (9)
1. a preparation method for mullite oxidation resistant coating, is characterized in that, comprises the steps:
Step one
With aluminum soluble salt, silicon ester be raw material, in molar ratio, Al:Si: organic solvent: catalyzer=(2 ~ 3): (1 ~ 1.5): (4 ~ 9): (0.3 ~ 0.5), joins and carries out back flow reaction after getting raw material, organic solvent, catalyzer and obtain gel; Gained gel after drying, under an oxygen-containing atmosphere in 1200-1350 DEG C of calcining, obtains precalcining porzite powder A;
Step 2
With aluminum soluble salt, silicon ester be raw material, in molar ratio, Al:Si: organic solvent: catalyzer=(2 ~ 3): (1 ~ 1.5): (4 ~ 9): (0.3 ~ 0.5), join after getting raw material, organic solvent, catalyzer and carry out back flow reaction at 60-85 DEG C, and then instill deionized water; And be warming up to 80 ~ 85 DEG C of reactions cooling, ageing after at least 8 hours; After ageing, 80 ~ 120 DEG C of dryings, obtain mullite precursor powder material B;
Step 3
In mass ratio, precalcining porzite powder A: mullite precursor powder material B=4 ~ 6:1, join and get precalcining porzite powder A, mullite precursor powder material B, then join and get film coalescence aid, drying retarder, solvent; By join get precalcining porzite powder A, mullite precursor powder material B, film coalescence aid, drying retarder, solvent evenly after obtain slurry, matrix is immersed in slurry, utilizes Best-Effort request technology to carry out slurry coating; After having applied, 1480 ~ 1515 DEG C of calcinings, obtain mullite oxidation resistant coating.
2. the preparation method of a kind of mullite oxidation resistant coating according to claim 1; It is characterized in that: in step one,
Described aluminum soluble salt is selected from the one in nine water aluminum nitrates, six water and aluminum chloride; The water reacting required in step one is provided by the crystal water in aluminium salt;
Described silicon ester is selected from least one in tetraethoxy, methyl silicate, positive silicic acid propyl ester;
Described organic solvent is selected at least one in dehydrated alcohol, anhydrous methanol; Described catalyzer is selected from least one in Glacial acetic acid and hydrofluoric acid.
3. the preparation method of a kind of mullite oxidation resistant coating according to claim 1; It is characterized in that:
In step one, described back flow reaction is: under 45-75 DEG C of heating in water bath, be warming up to 80-100 DEG C of reaction 10-14h after back flow reaction 3-5h again, obtain gel.
4. the preparation method of a kind of mullite oxidation resistant coating according to claim 3; It is characterized in that:
In step one, after obtaining gel, at 80-120 DEG C of dry 8-72 hour; With 150-350rpm after drying, after ball milling 1-4 hour, carry out calcining 2-3 hour at 1200-1350 DEG C, cool to room temperature with the furnace, obtain precalcining porzite powder A.
5. the preparation method of a kind of mullite oxidation resistant coating according to claim 1; It is characterized in that: in step 2;
Described aluminum soluble salt is selected from Burow Solution, Al (NO
3)
3at least one in 9H2O, Aluminum chloride anhydrous;
Described silicon ester is selected from least one in tetraethoxy, methyl silicate, positive silicic acid propyl ester;
Described organic solvent is selected at least one in dehydrated alcohol, anhydrous methanol;
Described catalyzer is selected from least one in Glacial acetic acid and hydrofluoric acid;
In the deionized water instilled and system, the mol ratio of aluminium element is 3 ~ 7:6.
6. the preparation method of a kind of mullite oxidation resistant coating according to claim 1; It is characterized in that: in step 2;
Back flow reaction 4 ~ 6h is carried out, then at instillation deionized water at 60-85 DEG C; And be warming up to 80 ~ 85 DEG C of reactions cooling, ageing after at least 8 hours; During ageing, the period is 1 ~ 2 month, temperature is 40-65 DEG C; After ageing completes, after 100-120 DEG C of dry 10-14h, after 1-4 hour, obtain mullite precursor powder material B with 150-350rpm ball milling.
7. the preparation method of a kind of mullite oxidation resistant coating according to claim 1; It is characterized in that: in step 3, in mass ratio, precalcining porzite powder A: mullite precursor powder material B=4 ~ 6:1, join and get precalcining porzite powder A, mullite precursor powder material B, and join 10 ~ 25wt% that the precalcining porzite powder A that gets and mullite precursor powder material B two kinds of powder total masses are solvent for use total mass; By join the 0.3-1.5% getting precalcining porzite powder A and mullite precursor powder material B total mass and join and get film coalescence aid; Described film coalescence aid is selected from least one in polyvinylpyrrolidone, polyvinyl butyral acetal; By 5 ~ 8wt% of solvent total mass, join and get drying retarder; Described drying retarder is selected from least one in oxalic acid, glycerol; Described solvent is selected from least one in dehydrated alcohol, anhydrous methanol, acetone.
8. the preparation method of a kind of mullite oxidation resistant coating according to claim 1-7 any one; It is characterized in that, comprise the following steps:
Steps A
In molar ratio, Al (NO
3)
3the mol ratio of 9H2O, tetraethoxy, dehydrated alcohol and Glacial acetic acid is 3:1:5 ~ 8:0.3 ~ 0.5, joins and gets Al (NO
3)
39H
2o, tetraethoxy, dehydrated alcohol and Glacial acetic acid, mix, and under 45-75 DEG C of heating in water bath, is then warming up to 80-100 DEG C of reaction 10-14h after back flow reaction 3-5h again, obtains gel; Gained gel is at 80-120 DEG C of dry 8-72 hour; With 150-350rpm after drying, after ball milling 1-4 hour, in atmosphere, carry out calcining 2-3 hour in 1200-1350 DEG C, cool to room temperature with the furnace, obtain precalcining porzite powder A;
Step B
In molar ratio, Burow Solution: Al (NO
3)
39H
2o: Aluminum chloride anhydrous: tetraethoxy=1.8:0.4:0.8:1; Join and get Burow Solution, Al (NO
3)
39H
2o, Aluminum chloride anhydrous, tetraethoxy;
Then, in molar ratio, glacial acetic acid: tetraethoxy=1 ~ 2:5 joins and gets glacial acetic acid,
The Burow Solution, the Al (NO that get will be joined
3)
39H
2o, Aluminum chloride anhydrous, tetraethoxy, glacial acetic acid are dissolved in dehydrated alcohol, under the environment of isolated moisture content, under 60-70 DEG C of heating in water bath after back flow reaction 3-5h, drip deionized water again, in the deionized water dripped and system, the mol ratio of aluminium element is 3 ~ 7:6, is warming up to 80-85 DEG C of reaction 8-12h subsequently; After reaction terminates by the gel that is obtained by reacting 40-65 DEG C of ageing 1 ~ 2 month, then after 100-120 DEG C of dry 10-14h to obtain mullite precursor powder material B after the rotating speed ball milling 1-4h of 200-300rpm; Burow Solution used, Al (NO
3)
39H
2in O, Aluminum chloride anhydrous, the mol ratio of aluminium element and dehydrated alcohol used is 3:5 ~ 8;
Step C
In mass ratio, precalcining porzite powder A: mullite precursor powder material B=4 ~ 6:1, join and get precalcining porzite powder A, mullite precursor powder material B, then join and get film coalescence aid, drying retarder, solvent; By join get precalcining porzite powder A, mullite precursor powder material B, film coalescence aid, drying retarder, solvent evenly after obtain slurry, matrix is immersed in slurry, utilizes Best-Effort request technology to carry out slurry coating; After having applied, 1480 ~ 1515 DEG C of calcinings, obtain mullite oxidation resistant coating; Described film coalescence aid is selected from least one in Polyvinylprrilone butyral, and the quality of used film forming auxiliary agent is the 0.8-1.2% of precalcining porzite powder A and mullite precursor powder material B total mass; Described solvent is made up of 7:3 ~ 5 by volume dehydrated alcohol and acetone, and join 10 ~ 25wt% that the precalcining porzite powder A that gets and mullite precursor powder material B two kinds of powder total masses are solvent for use total mass; Described siccative is oxalic acid, and consumption of oxalic acid is 5 ~ 8wt% of solvent total mass.
9. the preparation method of a kind of mullite oxidation resistant coating according to claim 8; It is characterized in that: when utilizing Best-Effort request technology to carry out slurry coating, the control rate of pulling is 05-3mm/min, and temperature is 40-50 DEG C.
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| CN108383132B (en) * | 2018-03-19 | 2021-07-16 | 华南理工大学 | Low-temperature preparation method of superfine mullite powder |
| CN111348939A (en) * | 2018-12-21 | 2020-06-30 | 通用电气公司 | EBC and mullite bond coat comprising non-oxide silicon ceramic |
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